Soluble oil



United States Patent SOLUBLE OIL James L. Jezl, Swarthmore, Pa., assignor to Sun Oil Company, Philadelphia, Pa., a corporation of New Jersey No Drawing. Application November 13, 1952, Serial No. 320,352

3 Claims. (Cl. 252-33.3)

This invention relates to soluble oil compositions comprising mineral oil, alkali metal soaps of carboxylicacids obtained by partial oxidation of mineral oil, and an added organic compound.

It is known in the art to prepare soluble oil compositions emulsifiable in water to form oil-in-water emulsions by forming a mixture of. mineral oil and alkali metal soap of carboxylic acids obtained by partialoxidation of mineral oil. Such compositions maybe calledfor convenience synthetic soluble oils, to distinguish them from soluble oil compositions which do not contain soaps of acidic products of oxidation of mineral oil. Major problems. involved in the preparation of synthetic soluble oil compositions have been the obtaining of a stable, homogeneous mixture of oil and soap prior to emulsification, and the obtaining of a stable emulsion after emulsification. The present invention provides a highly stable, homogeneous mixture of oil and soap, and a highly stable emulsion, these eifects being obtained by the incorporation in the soluble oil composition of an organic compound as coupling agent or mutual solvent, i. e., solvent for both oil and water. The organic compound employed has a dual function since it both stabilizes the soluble oil prior to ,emulsification and stabilizesthe emulsion after emulsification.

The organic compound employed in synthetic soluble oils according to the invention is a phenyl alkanol having 7to 9 carbonatoms inclusive. Suitable phenyl alkanols include phenyl methanol (i. e. benzyl alcohol), phenyl ethanol, phenyl-n-propanol, phenyl isopropanol, (2- methyl-phenyl) methanol, ethylphenyl methanol, etc.

It is to be noted that aromatic compounds having, a hydroxyl attached directly to the aromatic ring, are excluded from the scope of the present invention. It has been found that the latter compounds, e. g. phenol or cresol, are quite substantially inferior for use according to the invention as compared with benzyl alcohol for example, and are generally unsatisfactory for commercial use.

The soluble oil composition according to the present invention comprises mineral oil, alkali metal soap of, carboxylic acids obtainedby. partial oxidation of mineral oil, and a minor proportion ofan organiccompoundas specie fied above. It is generally preferred that the composition should also contain. other constituents suchas petroleum sulfonates and smallamounts of excess.alkali metal hydroxide and Water. In some cases, it may be desirable to incorporate alkali metal soap of petroleum naphthenic acids in the soluble oil. Also, in some cases, it may be desirable to incorporate in the soluble oil the entire product of oxidation of mineral oil, rather than just a predominantly carboxylic acid portion thereof.

Preferably the synthetic soluble oils according to the invention contain sulfonates in amount sufficient to provide a sulfonate saponification number equivalent of at least 3. Generally, the sulfonate saponification number equivalent is not greater than 10, more preferably not greater than 7. The sulfonate saponification number equivalent is deter- 2,770,594 Patented Nov. 13, 1956 mined by measurement, in mg. of KOH per gram, of the saponification number of the sulfonate-containing material prior to mixing with other saponifiable components of the soluble oil, and multiplying the saponifieation number thus obtained by the weight fraction of the sulfonatecontaining material in the compounded soluble oil.

Preferably, the concentration of carboxyl-containing materials in the soluble oils according to the invention is sutficient to provide a carboxylate saponification number equivalent of at least 10, more preferably at least 14. Generally, the carboxylate saponification number equivalent is not greater than 20, more preferably not greater than 17. The carboxylate saponification number equivalent may be determined in a manner generally similar to that described for determination of sulfonate saponification number equivalents.

The synthetic soluble oils according to the invention are preferably alkaline, having for example free alkalinity within the range 0.01 to 0.12 percent as NaOl-I.

The mineral lubricating oil employed in the soluble oil composition according to the invention preferably has S. U. viscosity at F. within the range from 40 to 120. The mineral oil Which is used as oxidation charge, on the other hand, preferably has S. U. viscosity at 100 F. within the range from to 200. A preferred oxidation charge is petroleum foots oil, but mineral lubricating oils may also be used. Mineral oil, as the term is used in connection with the oxidation charge, is understood to include petroleum wax, preferably paraflin wax having melting point not greater than 100 F, as well as normally liquid oils.

Petroleum foots oil is the oily byproduct obtained in the deoiling of slack wax. When the deoiling is done by sweating, the foots oil is sometimes called sweat oil or sweater oil. When the deoiling is done by filtration of a solution ofthe slack wax in a solvent for oil, the filtrate obtained is a solution of foots oil in the solvent used, e. g. methyl ethyl ketone or mixtures thereof with toluene and/or benzene. Petroleum foots oil generally contain substantial amounts of low-melting wax in addition to lu bricating oil, the amount of Wax depending on the filtration temperature and other variables.

The oxidation charge should have suificiently low content of aromatic compounds so that there is no substantial inhibition of the oxidation by aromatic compounds. Therefore, a preferred foots oil charge is one obtained from deoiling of slack wax from a solvent-refined lubrieating oil, e. g. a furfural-refined lubricating oil.

The oxidized mineral oil used in compositions according to the invention can be prepared in any suitable way. For example, it can be prepared by contacting the heated charge oil in liquid state with a free-oxygen-containing, gas, e. g. air, oxygen, ozonized air, etc. The oxidation is preferably conducted under atmospheric pressure or relatively low elevated pressure not exceeding, for example, 100 p. s. i. g. Such operation is advantageous in that the .vent gases carry oif some of the lower-boiling acidic products, which are undesirable in the soluble oil, and.

which in operation at higher pressures would remain in the liquid oxidation product. The oxidation is preferably conducted in the presence of an oxidation catalyst, such as.manganesenaphthenate, manganese soaps of fatty acids, manganesesoaps of carboxylic acids obtained in previous oxidations of mineral oil, etc.

The oxidation preferably-is continued at least until the saponification number of the liquid oxidation product is 60, and is terminated before the. saponification number of the. liquidoxidation product exceeds 120, preferably before the, saponification number exceeds 100. Oxidation to toohigh a .saponification number tends to result in for mationof oxidation products whichhave adverse effect on the soluble oil.

The organic compound employed according to the invention as a coupling agent or mutual solvent for synthetic soluble oils may be used if desired in conjunction with other coupling agents or mutual solvents, e. g. monobutyl ether of ethylene glycol. Also, mixtures of two or more coupling agents according to the present invention may be employed.

A preferred range of coupling agent concentration in the soluble oil according to the invention is from 1.25 to 3.0 volume percent. A preferred range of water concentration in the soluble oil is from 2.25 to 5.0 volume percent. Generally, for a given soluble oil there should be at least a certain amount of coupling agent to obtain satisfactory results, but this amount varies for different properties and relative proportions of the other constituents of the soluble oil. Also, there should generally, for satisfactory results, be a water content within certain upper and lower limits, but these limits also vary for different properties and relative proportions of the other constituents of the soluble oil.

The following examples illustrate the invention:

Example 1 Synthetic soluble oils were prepared by mixing the following materials in the stated amounts:

Mineral lubricating oil grams 490 Partially oxidized petroleum foots oil do 108 Petroleum naphthenic acids do 140 Petroleum mahogany sulfonates (10.9% solution in mineral oil) grams 250 Caustic soda, 50 B mi1liliters l7 adjusting the water content of the soluble oil at various levels, and adding benzyl alcohol in various concentrations.

The lubricating oil used had S. U. viscosity at 100 F. of about 100. The naphthenic acids had saponification number of 61. The petroleum sulfonates were sodium soaps of mahogany sulfonic acids having saponification number of 13.2 and contained 1.80 weight percent organic $03.

The oxidized foots oil was prepared by partially oxidizing a foots oil obtained in the solvent deoiling of slack wax, the oxidation being performed at 260320 F. and atmospheric pressure by blowing air through the foots oil containing a manganese-naphthenate-containing catalyst. The oxidation was continued until the saponification number of the liquid oxidation product was 78, and 108 grams of that product were then incorporated in the soluble oil.

The naphthenic acids and oxidized foots oil each contributed 8.5 saponification number equivalent to the soluble oils, and the sulfonates contributed 3.3 saponification number equivalent. The compounded soluble oil had free alkalinity of about 0.09-0.10 percent as NaOH.

Each soluble oil composition was tested for stability by allowing it to stand at 10 F. for 48-72 hours and then observing the soluble oil at room temperature to determine whether any oil had separated from the soluble oil to form an upper oil layer, and whether there were any signs of haziness or gelation in the soluble oil. Each soluble oil was rated as stable if there were no discernible oil separation, haziness, or gelation; otherwise, unstable.

Each soluble oil was also tested for emulsion stability by emulsifying 10 ml. of soluble oil in 90 m1. of added 45 F. tap water having calcium hardness less than 100 p. p. m. as CaCOs, and allowing the emulsion to comes to room temperature while standing for 24 hours, at the end of which time the appearance of the emulsion was observed to determine whether or not it was stable. If the emulsion surface was bright, or if it was only slightly dull, with very little or no cream on the surface, the emulsion was rated stable. If there was a substantial amount of cream or scum or free oil on the emulsion surface, the emulsion was rated unstable.

The following table shows the results obtained with various combinations of water content and benzyl alcohol content:

Vol. Per- Vol. Percent cent Oil Sta- Emulsion Water Benzyl bility Stability Alcohol Comparison example Synthetic soluble oils were prepared and tested in the same manner disclosed in Example I except that in each of five sets of experiments, a different hydroxy aromatic compound was used in place of benzyl alcohol. The five coupling agents used were phenol, o-cresol, m-cresol, pcresol, and cresylic acid. Each coupling agent was tested in various combinations of water content and coupling agent content Within the ranges 2.0 to 4.0 volume percent water and 1.5 to 2.0 volume percent coupling agent. In no case was a stable emulsion obtained. Comparison of these results with those obtained in Example I, shows that, for satisfactory results, the compound used must have at least one methylene group between the hydroxyl and the aromatic ring.

Example 11 Synthetic soluble oils as described in Example I, containing benzyl alcohol as coupling agent, were tested for hard water emulsion stability by emulsifying 10 parts by volume of the soluble oil in parts by volume of 45 F. hard water containing 300 p. p. m. of calcium hardness as CaCOs and p. p. In. of chloride hardness as NaCl, and allowing the emulsion to come to room temperature while standing for 24 hours, at the end of which time each emulsion was rated for stability. If the emulsion surface was bright, or if there was only slight cream or scum on the surface the emulsion was rated stable. If there was heavy cream or scum or free oil on the emulsion surface, the emulsion was rated unstable. The tap water emulsions as prepared in the preceding examples are rated somewhat more rigorously than the hard water emulsions of the present example, since hard water emulsions generally tend to be less stable than tap water emulsions, and a higher standard must therefore be used for tap water emulsions, in order to provide that in the majority of instances a given soluble oil which gives satisfactory tap water emulsions will also give satisfactory hard water emulsions.

The following results were obtained, oil stalbilities having been observed after one month at 70 F.

V01. V01. Percent Percent Oil Emulsion Water Coupling Stability Stability Agent 2. 6 1. 5 2. 6 1. 75 D 2. 6 2. 0 3. 0 1. 75 3. 0 2. 0 3. 4 2. O 3. 6 2.0 .do Do.

This table shows that highly satisfactory hard water emulsions are obtainable with synthetic soluble oils containing benzyl alcohol as coupling agent.

The properties of the oxidation product which is employed in synthetic soluble oils affects substantially the ease with which oil stability and emulsion stability can be imparted to the soluble oil by use of a coupling agent. The coupling agents according to the invention are particularrly advantageous in that they are capable of imparting oil stability and emulsion stability to synthetic soluble oils which contain an oxidation product which makes the soluble oil relative quite diflicult to stabilize.

The invention claimed is:

1. A soluble oil composition comprising: mineral lubricating oil; alkali metal soap of petroleum mahogany sulfonic acids; alkali metal soap of carboxylic acids obtained by partial oxidation of mineral oil; 2.25 to 5.0 volume percent of water; and 1.25 to 3.0 volume percent of a phenyl alkanol having 7 to 9 carbon atoms inclusive; said soluble oil having sultonate sapon-itication number equivalent within the range from 3 to 10 mg. of KOH per gram and carboxylate saponification number equivalent within the range from 10 to mg. of KOH per gram.

2. A soluble oil composition comprising: mineral lubrieating oil; alkali metal soap of petroleum mahogany sulfonic acids; alkali metal soap of carboxylic acids obtained by partial oxidation of mineral oil; 2.25 to 5.0 volume percent of water; and 1.25 to 3.0 volume percent of benzyl alcohol; said soluble oil having sulfonate saponification number equivalent within the range from 3 to 10 mg. of KOH per gram and carboxylate sap-onification number equivalent within the range from 10 to 20 mg. of KOH per gram.

'3. A soluble oil composition comprising: mineral lubrieating oil having S. U. viscosity at 100 F. within the range from to 120 seconds; alkali metal soap of petroleum mahogany sulfonic acids; alkali metal soap of petroleum naphthenic acids; a saponified oxidation product mixture obtained by partially oxidizing petroleum foots oil in liquid phase at a temperature in the range from 260 F. to 320 F. and a pressure from atmospheric to p. s. i. g. in the presence of a metallic oxidation catalyst until the saponification number of the oxidation product mixture is within the range from 60 to mg. of KOH per gram, and saponifying said oxidation product mixture with an alkali metal basic compound; 2.25 to 5.0 volume percent of water; and 11.25 to 3.0 volume percent of a phenyl alkanol having 7 to 9 carbon atoms inclusive; said soluble oil having sult'ona'te saponification number equivalent within the approximate range from 3 to 10 mg. of KOH per gram and carboxylate saponification number equivalent within the approximate range from 10 to 20 mg. of KOH per gram, approximately half of said carboxylate saponification number equivalent be ing supplied by said oxidation product mixture.

References Cited in the file of this patent UNITED STATES PATENTS 2,043,922 Burwell June 9, 1936 2,265,799 Carlson Dec. 9, 19441 2,470,913 *Bjorksten Mar. 24, 1949 FOREIGN PATENTS 587,279 Great Britain Apr. 21, 1947 633,517 Germany July 29, 1936 OTHER REFERENCES Metal Working Luba icants by Bastian, McGraw-I-Iill Pub. Co. 19541. i 

1. A SOLUBLE OIL COMPOSITION COMPRISING: MINERAL LUBRICATING OIL; ALKALI METAL SOAP OF PETROLEUM MAHOGANY SULFONIC ACIDS; ALKALI METAL SOAP OF CARNOXYLIC ACIDS OBTAINED BY PARTIAL OXIDATION OF MINERAL OIL; 2.25 TO 5.0 VOLUME PERCENT OF WATER; AND 1.25 TO 3.0 VOLUME PERCENT OF A PHENYL ALKANOL HAVING 7 TO 9 CARBON ATOMS INCLUSIVE; SAID SOLUBLE OIL HAVING SULFONATE SAPONIFICATION NUMBER EQUIVALENT WITHIN THE RANGE FROM 3 TO 10 MG. OF KOH PER GRAM AND CARBOXYLATE SAPONIFICATION NUMBER EQIVALENT WITHIN THE RANGE FROM 10 THE 20 MG. OF KOH PER GRAM. 